Synthesis and physical properties of estolides from lesquerella and castor fatty acid esters

Biodegradable, vegetable oil-based lubricants must have better low temperature properties as well as comparable cost to petroleum oils before they can become widely acceptable in the marketplace. The low temperature property usually measured is the pour point (pp), the minimum temperature at which the material will still pour. Viscosity and viscosity index also provide information about a fluid's properties where a high viscosity index denotes that a fluid has little viscosity change over a wide temperature range. Lesquerella oil is a good candidate for its development into a biodegradable lubricant as it is being developed as an alternative crop for the southwestern U.S. The hydroxy site on the fatty acid (FA) makes it a suitable site for esterification to yield estolides. Castor and lesquerella FA esters were combined with different types of saturated, unsaturated, and branched FAs to produce estolides. Castor and lesquerella estolide esters had the best cold temperature properties when capped with oleic (pp = −54 °C for castor and pp = −48 °C for lesquerella) or capped with a branched material, 2-ethylhexanoic acid (pp = −51 °C for castor and pp = −54 °C for lesquerella). As the saturation was increased in the estolide, pour and cloud points also increased. The increased saturation such as in stearic capped estolides allowed for sufficient alkyl stacking of these long saturated chains producing higher pour points. Oxidative stability of the estolides was compared between the oleic-castor estolide 2-ethylhexyl ester and the coco-castor estolide 2-ethylhexyl ester by the rotating bomb oxidation test (RBOT). The RBOT times for both estolides were low with a similar time of about 15 min. However, when the antioxidant package (3.5 wt.%) was added, the RBOT times increased to 403 min for the coco-castor estolide 2-ethylhexyl ester while still retaining its outstanding cold temperature properties, (pp = −36 °C and cp = −30 °C). The viscosity index ranged from 164 to 200 for these new hydroxy FA derived estolide 2-ethylhexyl esters. These oleic-castor and lesquerella estolide esters have displayed far superior low temperature properties (pp = −54 °C) than any other estolides reported to date. Due to the lack of solvent and catalysts, the cost of these estolides should be reasonable and more suitable as a base stock for biodegradable lubricants and functional fluids than current commercial materials.